JP6997917B1 - Three-dimensional modeling cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a three-dimensional shapeable cured product which can control the hardness after solidification, has excellent bondability with a face material, an aggregate and the like, and can be freely bent after curing. PROBLEM TO BE SOLVED: To add a specific curing agent B (curing agent B is calcium hydroxide, sodium hydrogencarbonate, myoban, magnesium chloride, etc.) to a main agent A containing an aqueous resin emulsion, an extender pigment and a dispersant. A three-dimensional molded product obtained by mixing 2 to 20 parts by mass of the curing agent B with respect to 100 parts by mass. [Selection diagram] FIG. 8

Description

The present invention relates to a three-dimensionally formable cured product that controls the hardness after solidification, has excellent bondability with a face material, an aggregate, and the like, and has excellent flexibility that can be freely bent after curing.

Painting and sculpture are two ways to express a three-dimensional object in the art field. In painting, there is a method of expressing a three-dimensional object on a plane such as a canvas by applying the optical illusion of light and shade and shade of color tones using paint, but it is not a three-dimensional object.
On the other hand, in the field of sculpture, there is a technique of carving a block of wood, stone, soil, metal, etc. to express the shape of an object three-dimensionally, and a technique of sculpting by arranging plastic materials to form a shape. In addition, clay and dry lacquer, which have been used since ancient times, are conventional materials that can be shaped three-dimensionally. Clay is made of layered silicate minerals that, when kneaded, can be agglomerated, stretched or crafted, and have the property of withstanding fire.
Dry lacquer is one of the techniques of lacquering. It is a method of laminating linen cloth or Japanese paper with lacquer and kneading lacquer and wood powder to form it, and it is mainly used for making utensils, caskets, and statues.
In addition, since the appearance of synthetic resin as a modeling material, modeling methods such as fiber reinforced plastic and stereolithography have been used. Fiber reinforced plastic, also called FRP, is a reinforced plastic in which fibers such as glass fiber and carbon fiber are compounded with epoxy resin, phenol resin, etc. to improve the strength. Stereolithography is a technology for creating a precise three-dimensional object that is exactly the same as 3D data by curing a liquid ultraviolet curable resin using an ultraviolet laser of an optical modeling device and laminating it.
All of the three-dimensional objects formed by the above various techniques lack flexibility, take time to produce, and have the disadvantages that no one can easily handle them.

As one of the three-dimensional modeling methods, "plaster" has been used for buildings from the past. Stucco is kneaded by mixing slaked lime and sand with water, and has been used in archaeological sites such as Mesopotamia, Greece, and Rome since BC. Fresco painting from this era is a method of painting plaster on a base such as a wall and drawing a picture with water-based paint dissolved in water before it dries, and fresco means "fresh". , It is a method to finish the picture while the plaster is still dry. This manufacturing method has the limitation that the production time is short.
Japanese plaster is made by mixing slaked lime with organic substances such as aggregate, hemp, and seaweed paste. Since it is a waterproof and non-combustible material, it has long been used as an external protective material for earthen walls, and as a topcoat material for the inner and outer walls of buildings made of wood and soil, such as castles, temples, merchant houses, private houses, and storehouses. .. Stucco is a so-called air-hardening material in which calcium hydroxide, the main component, hardens (carbonates) while absorbing carbon dioxide in the air, so it hardens over many years after moisture drying after construction. It is also a material to go. Since the calcium carbonate is insoluble in water, the stucco has a high shelf life.
This slaked lime (calcium hydroxide) hardened plaster has a certain yield strength but lacks flexibility and is therefore brittle and cannot withstand external pressure or impact. Stucco is mainly used for walls, and there are some relief-shaped wall decorations called "iron paintings", but there are no examples of it being used for independent three-dimensional objects.

To give an example of a modeling material capable of three-dimensional expression, in Patent Document 1, the fluidity that can be easily squeezed out through a squeezing port having a predetermined shape and the predetermined shape of the squeezing port are maintained as they are. International Publication No. 2007/055257 (Patent Document 1) discloses a creamy lightweight modeling material that has excellent shape retention to the extent that it can be used, eliminates the problem of swelling, and provides excellent storage stability. There is. However, with this material, there is a problem that the hardness and flexibility of the modeling material after drying are determined by the composition of the modeling material, and the hardness and flexibility cannot be freely controlled.

Clay, which has been used since ancient times, is composed of fine particles of silicate minerals, and is extremely excellent in three-dimensional modeling by adding water and kneading. However, since the strength after drying is extremely vulnerable to tension and impact, it is generally used as pottery or pottery by baking it at a high temperature.
In recent years, products made from wheat flour, agar, beeswax, etc. have begun to spread. All of these clays are excellent in formability, but have the drawback of not being able to withstand a small impact because they are not elastic.

Dry lacquer ware is also a modeling material that has been used since ancient times, and dry lacquer ware, which is one of the techniques using lacquer, is a method of laminating linen cloth or Japanese paper with lacquer and kneading lacquer and wood powder to form it. It was used to model Buddhist statues and vessels. After curing, it is fairly hard and tough, but flexibility is not required. This method has the disadvantages that it takes a long time to produce because it takes a long time for the lacquer to solidify, and that the lacquer material is expensive because the amount of production is limited in modern times.
In addition, FRP, which is one of the methods of curing synthetic resin to form it, emits a strong odor peculiar to synthetic resin at the time of production, has high impact resistance but lacks flexibility, and the stereolithography method is special. Since it requires a device and data must be input, it is not possible for anyone to handle it freely, such as requiring a certain level of technical acquisition to handle the device.

On the other hand, it is disclosed in Japanese Patent No. 4548631 (Patent Document 2) that a flake-shaped glass is coated with a metal or the like as a pigment in order to give a three-dimensional effect with an oil paint. However, this method has a problem that the three-dimensional effect is not large and the cost is high. Further, the cured paint is not elastic and has a hard texture.

Further, Japanese Patent Application Laid-Open No. 2007-9040 (Patent Document 3) discloses a method of producing a thick texture like an oil painting because the drying time is fast and there is no odor, and the workability is excellent. Although the paint was elastic, it did not have a three-dimensional effect that greatly exceeded that of oil paint.

As a method for producing a reproduction of a three-dimensional painting, an organic binder, calcium hydroxide having a specific particle size (10 μm) or less, and an inorganic powder having a specific particle size (5.0 μm) or less are placed on a substrate sheet. A technique for forming an unevenness reproduction layer having unevenness reflecting the unevenness of the original painting by using the contained slurry-like mixture and printing the painting on the unevenness by inkjet is published in International Publication No. 2016/039354 (Japanese Patent Publication No. 2016/039354). It is disclosed in Patent Document 4). In general, in paintings, it is unlikely that an external pressure will be applied to the uneven layer. Therefore, Patent Document 4 does not clearly describe the properties of the strength surface of the uneven layer, but as an expression related to the strength, [ 0025], "The base sheet 1 has flexibility (partially omitted), and effectively suppresses inconveniences such as the formation of cracks in the unevenness reproduction layer 3 provided on the base sheet 1. It can be done. " From this expression, it is presumed that the uneven layer of Document 4 has a brittle property in which cracks are likely to occur.

Japanese Patent Application Laid-Open No. 2012-81388 (Patent) relates to a wall surface finishing method for shortening the drying time by adding an alkaline earth metal oxide having water reactivity to an acrylic resin emulsion as an undercoat, which is related to a building finish coating material. It is disclosed in Document 5). Patent Document 5 covers the formation of a wall surface, and does not disclose the properties of the composition other than promoting drying.

International Publication No. 2007/05257 Japanese Patent No. 4548631 Japanese Unexamined Patent Publication No. 2007-9040 International Publication No. 2016/033954 Japanese Unexamined Patent Publication No. 2012-81388

An object of the present invention is to provide a three-dimensionally formable cured product that controls the hardness after solidification, has excellent bondability with a face material, an aggregate, etc., and has excellent flexibility that can be freely bent after curing. It is to do, and it provides a method of producing it.
In addition, it is to provide a cured product that can form a three-dimensional painting or a relief-like model by forming a texture thicker than an oil painting and controlling the hardness of the paint after drying. It provides the production method.

As a result of diligent studies to solve the above-mentioned problems, the present inventor adjusts a specific amount of a specific curing agent B and mixes it with the main agent A containing an aqueous resin emulsion, an extender pigment and a dispersant. Not only the hardness after curing, but also the maximum point elongation and maximum point weighting in the tensile test can be adjusted, the surface does not crack even when bent or pulled, and free bending is possible. He found that he could obtain a product, and completed the present invention.

That is, the present invention is a three-dimensional molded product obtained by mixing and solidifying [1] main agent A and curing agent B.
The main agent A contains an aqueous resin emulsion, an extender pigment, and a dispersant.
The resin of the aqueous resin emulsion is at least one selected from the group consisting of acrylic resin, acrylic acid ester copolymer, vinyl acetate resin, alkyd resin, phthalic acid resin, and urethane resin.
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogencarbonate, myoban, and magnesium chloride, and the amount of the curing agent B added is 100 parts by mass of the main agent A. It is a three-dimensional molded product, characterized in that the agent B is 2 to 20 parts by mass.

Further, in the present invention, [2] the extender pigment is at least one selected from the group consisting of aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, alumina silicate, titanium oxide and zinc oxide. The cured product according to [1], wherein the amount of the extender pigment added is 30 to 70% by mass based on the total amount of the main agent A.

Further, the present invention is characterized in that [3] the dispersant is a polyacrylic acid-based dispersant, and the amount added is 1 to 10% by mass with respect to the total amount of the main agent A, [1] or [ 2] is the cured product according to.

Further, the present invention is characterized in that [4] the maximum point elongation (% GL) in the tensile test of the cured product is 30% to 100%, any one of [1] to [3]. It is a cured product according to.

Further, the present invention is characterized in that [5] the hardness of the cured product is 20 to 50 in a durometer hardness test (type C), whichever is one of [1] to [4]. It is a cured product according to.
It is a thing.

Further, in the present invention, [6] the main agent A contains an aqueous resin emulsion, an extender pigment and a dispersant.
The resin of the aqueous resin emulsion is at least one selected from the group consisting of acrylic resin, acrylic acid ester copolymer, vinyl acetate resin, alkyd resin, phthalic acid resin, and urethane resin.
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogen carbonate, alum, and magnesium chloride.
A coating agent in which 2 to 20 parts by mass of the curing agent B is mixed with 100 parts by mass of the main agent A is used.
(I) Metal / non-ferrous metal / plastic wire rod, metal / non-ferrous metal / plastic mesh material, or a three-dimensional member selected from bamboo or wood strip, or the surface of the member such as paper, cloth, non-woven fabric, aluminum foil, etc. A member whose surface is covered with a material; or (ii)
Metal / non-ferrous metal, glass, carbon, synthetic resin, bamboo, wood, paper, cloth, etc., linear or ribbon-shaped (thin strip with a certain width), net, surface-shaped core material, steel wire or A metal or non-ferrous metal wire such as aluminum or copper is wound multiple times to a certain diameter, stretched in the axial direction of the circle, the outer shape of the winding becomes spiral, and a non-woven cloth or synthetic resin is wrapped around the spiral. Attached pipe members; or (iii) thin plates of wood or bamboo, one side of paper, or both members;
It is a method for producing a three-dimensional model, which is characterized in that it is applied to the surface or between the surfaces of the above and cured to form a cured product that can be deformed.

Further, in the present invention, [7] the main agent A contains an aqueous resin emulsion, an extender pigment and a dispersant.
The resin of the aqueous resin emulsion is at least one selected from the group consisting of acrylic resin, acrylic acid ester copolymer, vinyl acetate resin, alkyd resin, phthalic acid resin, and urethane resin.
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogen carbonate, alum, and magnesium chloride.
A coating agent in which 2 to 20 parts by mass of the curing agent B is mixed with 100 parts by mass of the main agent A is applied to the canvas, and can be freely deleted or deformed, or can be reapplied to create a painting or relief. It is a method of producing a painting, which is characterized by forming.

The three-dimensional molded product of the present invention is obtained by mixing the main agent A and the curing agent B and curing them. Immediately after mixing the main agent A and the curing agent B (this state is referred to as the "coating agent" of the present invention), the hardness is slurry-like or soft clay, and it is kneaded into a certain mold or it. After recoating itself, it solidifies to form a cured product with the desired thickness, and not only hardness but also maximum point elongation and maximum point weighting can be adjusted as appropriate, and surface cracking is also possible against bending and pulling. It is possible to mold it as a three-dimensional model with excellent flexibility that allows free bending.
In addition, paper, cloth, non-woven fabric, and aluminum foil are used for rough three-dimensional members made of relatively strong materials such as metal / non-ferrous metals, wires such as plastics, mesh materials, bamboo, and wood. It is also possible to cover the surface with a face material such as the above, apply the coating agent according to the present invention to a certain thickness, and cure the coating material to create an appearance shape as a three-dimensional model.

Although it is not possible to deform the modeled product by the conventional modeling method, it is possible to freely deform and model the product after it is cured by using the cured product or the production method of the present invention. For example, when metal or non-ferrous metal is used as an aggregate, the surface of the cured product is rubbed with a spatula with a curved surface (deformed by applying pressure) to form irregularities in a desired shape by taking advantage of the plastic deformation. can.
Among the decorations and tools used in temporary installations such as shows, events, and theater sets, for example, when making a three-dimensional object such as a large rock, the frame for making it three-dimensional and the surface on it should be placed. It is also possible to create.

Further, by using the cured product of the present invention, for example, in the case of a synthetic resin pipe, a steel wire or a metal / non-woven metal wire such as aluminum / copper is wound multiple times to a certain diameter and wound in the axial direction of the circle. When stretched to, the outer shape of the winding becomes spiral, and a cloth (or a non-woven fabric made of synthetic resin) is wrapped around the spiral, and the curing agent of the present invention is used on the cloth to easily form a pipe. be able to.
This pipe is expected to be used in various ways. For example, in stage decoration, it can be used as a trunk of a tree, as a decoration bent like a snake, as a work of art in which the side surface of a pipe is deformed, and as a functional member, as a water pipe or a ventilation duct.

Further, the cured product of the present invention includes, for example, waterproof gloves / boots, a water tank, etc. for waterproof materials, and is applied to one side of wood, bamboo thin plate or paper, or between both of them for those requiring flexibility. Then, it can be applied to the production of extremely flexible surfaces.

Since the main agent A imparts strong adhesiveness to itself, it has good adhesion to the coated surface, and the material cured by adding the curing agent B to the main agent A is somewhat similar to rubber. Since it is elastic, it does not crack or peel off, and it can withstand bending, so that when it is applied to a structure, it is possible to form a shaped object that follows the structure. Further, the coating agent has a strong adhesiveness and an adhesive force to an object that comes into contact with the coating agent before curing, but has a property that the surface after curing has no adhesiveness at all. It also has excellent waterproof properties after curing.

Furthermore, in paintings, in the case of expressing the shape of wave swell or sharp unevenness by using coating agents with different mixing ratios of the main agent A and the curing agent B in the three-dimensional wave part and rock part. By properly expressing the shape of a rock with a certain shape, it is possible to create a shape that expresses the characteristics of the desired shape with a painting knife for both the wave part and the rock part. For example, about 2 hours after the start of mixing the main agent A and the curing agent B, it is still at the start of curing, and it can be freely deleted and deformed, and after 6 hours, it is in a semi-cured state to the extent that it does not deform. Since it can be freely expressed, the adhesiveness of the surface is lost 6 hours after the start of mixing the main agent A and the curing agent B, and it is possible to maintain the same storage state as the conventional oil painting.

Further, since the main agent A is water-based, it is possible to mix commercially available acrylic paints and water-based paints, so that it is possible to freely create a color tone suitable for the purpose of expression. In addition, since it is possible to freely obtain materials having different curing speeds and elasticity corresponding to the amount of the curing agent B added, it is possible to form relief-shaped paintings and three-dimensional modeling, so that it is possible to provide a cured product with rich expression. Can be done.

The figure which shows the time-dependent change of the addition amount of the curing agent B, and the hardness [durometer]. The figure which shows the time-dependent change of the addition amount of the curing agent B, and the reduction rate of the water content in the main agent A. The figure which shows the influence of the curing agent B on the relationship between the amount of water evaporation in the main agent A and the hardness [durometer]. Process diagram in which the main agent A and the curing agent B are arranged on the pallet. A process diagram showing a state in which the main agent A and the curing agent B are mixed with a painting knife C. A process diagram in which a mixture of the main agent A and the curing agent B is applied to a model made of steel wire with a painting knife D. The figure which completed the painting process of FIG. After the modeled object shown in FIG. 7 is cured, the modeled object is shaped into an arbitrary shape. A model in which a mixture of the main agent A and the curing agent B is applied to an icosahedron model made of steel wire with a painting knife D. The figure which deformed the model of FIG. Diagram showing an example of rock production The figure which shows the example which attached the cloth (nonwoven fabric) to the wire mesh and applied the coating agent. The figure which shows the manufacturing example of a pipe Painting using a three-dimensional molded product according to the present invention

In the present invention, by adjusting a specific amount of a specific curing agent B and mixing it with a main agent A containing an aqueous resin emulsion, an extender pigment and a dispersant, not only the hardness after curing but also the maximum point elongation and the maximum point are achieved. The present invention relates to a three-dimensional molded product having excellent flexibility, which can be adjusted in weight, etc., does not crack on the surface even when bent or pulled, and can be freely bent. Hereinafter, embodiments for carrying out the present invention will be described. The present invention is not limited to the following description.

[1] The first aspect of the present invention is a three-dimensional molded product obtained by mixing and solidifying a main agent A and a curing agent B.
The main agent A contains an aqueous resin emulsion, an extender pigment, and a dispersant.
The resin of the aqueous resin emulsion is at least one selected from the group consisting of acrylic resin, acrylic acid ester copolymer, vinyl acetate resin, alkyd resin, phthalic acid resin, and urethane resin.
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogencarbonate, myoban, and magnesium chloride, and the amount of the curing agent B added is 100 parts by mass of the main agent A. It is a three-dimensional molded product, characterized in that the agent B is 2 to 20 parts by mass.

[1-1] In the first-first aspect of the present invention, the aqueous resin emulsion is a styrene-butadiene polymer, a styrene-acrylic copolymer, a methylmethacryllate-butadiene polymer, vinyl acetate. -The three-dimensional molded product according to the above aspect [1], which is at least one selected from the group consisting of acrylic copolymers.

[1-2] The first and second aspects of the present invention are the three-dimensional molded product according to the above aspect [1], wherein the amount of the aqueous resin emulsion added is 5 to 40% by mass.

[1-3] In the first to third aspects of the present invention, the amount of the aqueous resin emulsion added is 10 to 30% by mass with respect to the total amount of the main agent A. Is.

[1-4] In the first to fourth aspects of the present invention, the amount of the aqueous resin emulsion added is 15 to 25% by mass with respect to the total amount of the main agent A. Is.

[1-5] In the first to fifth aspects of the present invention, the extender pigment comprises a group consisting of aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, alumina silicate, titanium oxide, and zinc oxide. The three-dimensional molded product according to the above aspect [1], which is at least one selected.

[1-6] In the first to sixth aspects of the present invention, the extender pigment is at least one selected from the group consisting of aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, silica, titanium oxide, and zinc oxide. This is the three-dimensional molded product according to the above aspect [1].

[1-7] The first-7th aspect of the present invention is the three-dimensional molded product according to the above aspect [1], wherein the amount of the extender pigment added is 25 to 75% by mass with respect to the whole main agent A. be.

[1-8] The first to eighth aspects of the present invention are the three-dimensional shaped cured product according to the above aspect [1], wherein the amount of the extender pigment added is 30 to 70% by mass with respect to the whole main agent A. be.

[1-9] The first to nine aspects of the present invention are the three-dimensional shaped cured product according to the above aspect [1], wherein the amount of the extender pigment added is 50 to 70% by mass with respect to the entire main agent A. be.

[1-10] The first to ten aspects of the present invention are the three-dimensional shaped cured product according to the above aspect [1], which is a combination of any of the above aspects [1-1] to [1-9]. be.

[2] The second aspect of the present invention is described in any one of the above aspects [1] to [1-10], wherein the dispersant is a polyacrylic acid-based dispersant. It is a three-dimensional molded product. Any combination of embodiments is possible.

[2-1] The second aspect of the present invention is characterized in that the amount of the dispersant added is 1 to 10% by mass with respect to the entire main agent A, the above aspects [1] to [1]. -10] The three-dimensional molded product according to any one of the embodiments.

[2-2] The second aspect of the present invention is characterized in that the amount of the dispersant added is 2 to 5% by mass with respect to the entire main agent A, the above aspects [1] to [1]. -10] The three-dimensional molded product according to any one of the embodiments.

[3] The third aspect of the present invention is characterized in that the maximum point elongation (% GL) in the tensile test is 30% to 100%, the above-mentioned aspects [1] to [1-10], and. [2] The three-dimensional molded product according to any one of [2-2]. Any combination of embodiments is possible.

[4] A fourth aspect of the present invention is characterized in that the maximum point load (N) in the tensile test is 55N to 100N, according to the above aspects [1] to [1-10], [2] to [. It is a three-dimensional molded product according to any one of 2-2] and [3]. Any combination of embodiments is possible.

[5] A fifth aspect of the present invention is the durometer hardness test (type C), wherein the aspect is 20 to 50, the above-mentioned aspects [1] to [1-10], [2] to [. The three-dimensional molded product according to any one of 2-2], [3], and [4]. Any combination of embodiments is possible.

[6] A sixth aspect of the present invention comprises a main agent A and a curing agent B.
The main agent A contains an aqueous resin emulsion, an extender pigment, and a dispersant, and the resin of the aqueous resin emulsion is an acrylic resin, an acrylic acid ester copolymer, a vinyl acetate resin, an alkyd resin, or a phthalic acid resin. It is at least one selected from the group consisting of urethane resins, and the amount of the aqueous resin emulsion added is 5 to 40% by mass based on the total amount of the main agent A;
The extender pigment is at least one selected from the group consisting of aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, alumina silicate, titanium oxide, and zinc oxide, and the amount of the extender pigment added is 30-70% by mass with respect to the total base material A;
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogencarbonate, myoban, and magnesium chloride, and the amount of the curing agent B added is 100 parts by mass of the main agent A. It is a three-dimensional molded product, characterized in that the agent B is 2 to 20 parts by mass.

[6-1] The 6-1 aspect of the present invention is the embodiment of the above aspects [1] to [1-10], [2] to [2-2], [3], [4] and [5]. It is a three-dimensional shaped cured product combined with any aspect of any aspect.

[7] In the seventh aspect of the present invention, the main agent A and the curing agent B according to any one of the above aspects [1] to [1-10] and [2] to [2-2] are mixed. Apply the coating agent,
(I) Metal / non-ferrous metal / plastic wire rod, metal / non-ferrous metal / plastic mesh material, or a three-dimensional member selected from bamboo or wood strip, or the surface of the member such as paper, cloth, non-woven fabric, aluminum foil, etc. A member whose surface is covered with a material; or (ii)
Metal / non-ferrous metal, glass, carbon, synthetic resin, bamboo, wood, paper, cloth, etc., linear or ribbon-shaped (thin strip with a certain width), net, surface-shaped core material, steel wire or A metal or non-ferrous metal wire such as aluminum or copper is wound multiple times to a certain diameter, stretched in the axial direction of the circle, the outer shape of the winding becomes spiral, and a non-woven cloth or synthetic resin is wrapped around the spiral. Attached pipe members; or (iii) thin plates of wood or bamboo, one side of paper, or both members;
It is a method for producing a three-dimensional model, which is characterized in that it is applied to the surface or between the surfaces of the above and cured to form a cured product that can be deformed.

[8] In the eighth aspect of the present invention, the main agent A and the curing agent B according to any one of the above aspects [1] to [1-10] and [2] to [2-2] are mixed. Apply the coating agent
It is a method of producing a painting, which is characterized in that a painting or a relief is formed by applying it to a canvas and freely deleting or deforming it, or by repainting it.

[9] In the ninth aspect of the present invention, the main agent A according to the embodiments [1] to [1-10], [2] to [2-2], and [3] to [8] is used. Further, it is a three-dimensional molded product or a production method, which contains a wetting agent and the addition amount thereof is 5% by mass or less.

[9-1] The ninth aspect of the present invention is a three-dimensional molded product or a production method, characterized in that the amount of the wetting agent added is 3% by mass or less.

Hereinafter, the present invention will be described in detail.
In the present invention, the "three-dimensional molded product" can adjust not only the hardness after curing but also the maximum point elongation and the maximum point weight, and the surface does not crack even when bent or pulled, and free bending is possible. It means a cured product with excellent flexibility.

In the present invention, the "coating agent" means a mixture of the main agent A and the curing agent B, particularly the state immediately after mixing, which is the hardness of a slurry or soft clay, which is kneaded into a certain mold. Alternatively, it is possible to obtain a desired thickness by recoating itself. Further, by adjusting the amount of the curing agent B with respect to the main agent A, not only the hardness but also the maximum point elongation and the maximum point weighting can be adjusted, and after the mixture is cured, the surface cracks even when bent or pulled. It is possible to bend freely without doing so, and it becomes a three-dimensional model with excellent flexibility. In order for the coating agent to be a three-dimensional molded product having a desired flexibility, it is preferable that 24 hours or more have passed after mixing, and it is more preferable that 48 hours or more have passed.

An indispensable element for producing the flexibility of the cured product of the present invention is the mixing ratio of the main agent A and the curing agent B, and the amount of the curing agent B added is 100 parts by mass of the main agent A. The curing agent B is 2 to 20 parts by mass. If it is less than 2 parts by mass, the curing time is long, and if it is more than 20 parts by mass, inconveniences such as inferior flexibility and cracking (significantly inferior in tensile strength) occur, and practicality is low.

In the present invention, "art" has the same meaning as plastic arts or plastic arts, and is a general meaning of paintings, prints, sculptures, architecture, crafts, and the like. In a narrower sense, it refers only to paintings, prints, and sculptures, but its characteristics are (1) established on space by (1) physical materials or means, and (3) the spatial figures formed are parallel to stillness. It becomes visible in the state of (Britanica International Encyclopedia Sub-item Encyclopedia).

Hereinafter, embodiments of the present invention will be described. It should be noted that the following embodiment is an embodiment of the present invention and does not limit the present invention to the scope thereof.
<Embodiment 1>
1. 1. Material according to Embodiment 1 (water-based resin emulsion)
The "aqueous resin emulsion" means a resin compound having many hydrophilic groups in the molecule, in which particles of synthetic resin are dispersed in water (O / W type emulsion). Examples of the resin used for the emulsion include acrylic resins, acrylic acid ester copolymers [styrene-acrylic copolymers, methylmethacryllate-butadiene-based polymers, vinyl acetate-acrylic copolymers], and the like. There are styrene-butadiene polymer, vinyl acetate resin, acrylic resin, phthalic acid resin, urethane resin and the like. Acrylic resin is a material (amorphous synthetic resin) having extremely high weather resistance and transparency among synthetic resins, and its basic skeleton is a polymer of acrylic acid ester or methacrylic acid ester.
From the viewpoint of dispersibility, water resistance and adhesion of the extender pigment, a styrene-butadiene polymer, a styrene-acrylic copolymer, a methyl methacrylate / butadiene polymer, and a vinyl acetate-acrylic copolymer are preferably used. To.
The amount of the aqueous resin emulsion added is usually 5 to 40% by mass, preferably 10 to 30% by mass, and more preferably 15 to 25% by mass with respect to the total amount of the main agent A in terms of solid content. be. When the addition amount is less than 5% by mass, the adhesiveness of the main agent A and the dispersibility of the quality pigment are inferior, and cracks may occur when the modeled product dries. There is also a problem with flexibility. On the other hand, if it exceeds 40% by mass, the color-developing property may decrease and the durability of the modeled object may be inferior.

Wetting agents may be added to stabilize the aqueous resin emulsion. As the wetting agent, for example, a water-soluble polyhydric alcohol is used, but ethylene glycol, propylene glycol, and glycerin are preferably used.
The amount of the wetting agent added is 5% by mass or less, preferably 3% by mass or less, based on the total amount of the main agent A. If it is 5% by mass or more, the drying property of the cured product of the present invention may be slowed down.

(Constitution pigment)
The extender pigment is a white to colorless pigment used as a bulking agent. For example, as the white pigment, aluminum hydroxide, calcium carbonate (light calcium carbonate, heavy calcium carbonate), magnesium carbonate, barium sulfate, silica, talc, alumina silicate, titanium oxide, zinc oxide and the like are used. These extender pigments may be used alone or in combination of two or more. More preferably, aluminum hydroxide, calcium carbonate (light calcium carbonate, heavy calcium carbonate), magnesium carbonate, barium sulfate, silica, titanium oxide, zinc oxide are used. The amount added is 25 to 75% by mass, preferably 30 to 70% by mass, and more preferably 50 to 70% by mass with respect to the total amount of the main agent A.

(Dispersant)
The surfactant contributes to the dispersion of the inorganic compound such as the extender pigment added to the aqueous resin emulsion in the solution. If the concentration of the inorganic compound is too high, the inorganic compound will aggregate in the aqueous resin emulsion. Therefore, a surfactant is added to prevent agglutination of these inorganic compounds in an aqueous solution.
Examples of such dispersants include polyacrylic acid. Examples of the polyacrylic acid-based dispersant include sodium polyacrylate, a carboxylate-based copolymer (sodium salt), a sulfonic acid-based copolymer (sodium salt), sodium polycarboxylate, ammonium polyacrylate, or poly. Examples thereof include acrylic acid-based polymers. More preferably, ammonium polyacrylate and a polyacrylic polymer are used. When the particle size of the inorganic compound is submicron and the specific surface area is large, a polyacrylic acid-based polymer can be used.
The amount of these dispersants added is preferably 1 to 10% by mass, more preferably 2 to 5% by mass, based on the total amount of the main agent A.

(Antibacterial / antifungal agent)
In this embodiment, zinc oxide is added to the main agent A as an antibacterial / antifungal measure. Zinc oxide acts as an antifungal and antibacterial agent. Therefore, even in a place where the humidity of the environment in which the cured product of the present invention or the model is installed is high, it is possible to suppress the generation of mold on the cured product or the model. This effect is higher as the particle size is smaller, and those having an average particle size of less than 1 μm are preferably used. In addition, zinc oxide has a high whiteness and also has a function as an extender pigment.

(UV blocking agent)
Further, titanium oxide was added to the main agent A according to the present embodiment as a measure against ultraviolet rays. In addition to acting as a fungicide and antibacterial agent, titanium oxide also has an ultraviolet ray blocking function and contributes to improving the durability of the modeled object. This effect is higher as the particle size is smaller, and those having an average particle size of less than 1 μm are preferably used. In addition, titanium oxide has a high whiteness and also has a function as an extender pigment (titanium white, titanium white (English: titanium white)).
As titanium oxide, a rutile type having low activity as a photocatalyst and excellent in thermal stability is used, and has a high ultraviolet hiding power. When exposed to a cured product, modeled object, or sunlight for a long period of time, the photocatalyst may cause discoloration or the modeled object to crack. To prevent this problem, the surface of titanium oxide is coated with an inorganic material. Will be done.

(Electrolytes)
An electrolyte that promotes a curing action was used in the curing agent B according to the present embodiment as the main agent A according to the present embodiment. An electrolyte is a substance that is dissolved in water and dissociates (ionizes) into ions in a solution to exhibit electrical conductivity. When an electrolyte is added to an aqueous resin emulsion, a phenomenon called salting out occurs, causing the aqueous resin emulsion to cure and water to separate.
As the electrolyte, potassium hydroxide, sodium hydroxide, calcium oxide [raw lime], calcium hydroxide [slaked lime], sodium hydrogen carbonate [boso], myoban, magnesium chloride, sardine, etc. are used, but the curing characteristics and economics , Calcium hydroxide, sodium hydrogen carbonate [sodium], myoban, magnesium chloride are suitable from the viewpoint of safety and the like.
The amount of the curing agent B added, which is an electrolyte that promotes the curing action, varies depending on the type of each electrolyte, but the main agent A is used in the range of 1 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass. It is a mass part. When the electrolyte is a polyvalent metal salt such as calcium ion, the addition amount is preferably 2 to 20 parts by mass.

As for the hardness of the cured product of the present invention, the hardness value of the durometer [C type] is preferably 15.5 to 52.5, more preferably 20 to 50.

The maximum point elongation (% GL) in the tensile test of the cured product of the present invention is also good for bending and tension, and is preferably 30% to 100% from the viewpoint of flexibility that allows free bending. ..

The maximum point load (N) in the tensile test of the cured product of the present invention is preferably 55N to 100N, more preferably 57N to 99N.

Next, Examples, Comparative Examples, and Test Examples will be given to explain the present invention in more detail, but these examples are merely embodiments, do not limit the present invention, and are the scope of the present invention. It may be changed within a range that does not deviate from.

(Aqueous resin emulsion, wetting agent)
The aqueous resin emulsion constituting the main agent A is a styrene-butadiene polymer emulsion (SBR; "Narsta-SR116" manufactured by Nippon AADL Co., Ltd., solid content 51%) and a methylmethacryllate-butadiene polymer emulsion (SBR). MBR; "Narsta-MR171" manufactured by Nippon AADL Co., Ltd., solid content 49%) was used.
As the wetting agent, polyethylene glycol (Hayashi Junyaku Kogyo Co., Ltd. "special grade") was used.

(Constitution pigment)
As the extender pigment constituting the main agent A, calcium bicarbonate (Calfine Co., Ltd. "aACE-30", average particle size: 0.9 μm), zinc oxide (HakusuiTech Co., Ltd. "ZINCOX SUPER F1", average particle size 0.1 μm) ), And titanium oxide (Sakai Chemical Industry Co., Ltd. “CTR-100”, average particle size 0.26 μm _, surface treatment ZrO2 ・_Al2O3 ) _were used. Zinc oxide is also an antibacterial and antifungal agent, and titanium oxide is also an ultraviolet blocking agent.

(Dispersant)
As the dispersant for calcium bicarbonate, Ammoniu polyacrylic acid (“Aron A-30SL, solid content 40%” manufactured by Toagosei Co., Ltd.) was used. As the dispersant for zinc oxide and titanium oxide, a polyacrylic acid-based polymer (“Aron SD-10, solid content 40%” manufactured by Toagosei Co., Ltd.) was used.

(Electrolytes)
As the curing agent B, calcium hydroxide (Hayashi Junyaku Kogyo Co., Ltd. “reagent”), baked alum (aluminum sulfate potassium / dried, Taiyo Pharmaceutical Co., Ltd.), and sodium hydrogen carbonate [baking soda] (reagent) were used.

<Adjustment of calcium carbonate related to main agent A>
Calcium carbonate (302.5 g), ammonium polyacrylate (13.75 g) and distilled water (300 g) are mixed with a homomixer (Plymix Co., Ltd. "mark-II", 2000 rpm for 10 minutes, and then at 108 ° C. After that, it was decomposed and crushed by a bead mill (IMEX Co., Ltd. "RMB") for 15 hours to obtain a calcium carbonate-treated powder.
<Adjustment of zinc oxide and titanium oxide related to main agent A>
Zinc oxide (16.5 g) and titanium oxide (16.5 g) are prepared, and a polyacrylic acid-based polymer (13.75 g) and distilled water (120 g) are mixed with a homomixer at 4000 rpm for 20 minutes, and then mixed. After drying at 108 ° C. for 2 hours, it was decomposed and crushed by a bead mill (IMEX Co., Ltd. “RMB”) for 30 to obtain treated powders of zinc oxide and titanium oxide.

<Adjustment of main agent A>
Styrene-butadiene polymer emulsion (95 g), methylmethacryllate butadiene polymer emulsion (95 g), polyethylene glycol (5 g), calcium carbonate-treated powder (275 g), zinc oxide-treated powder (15 g) and oxidation. The titanium-treated powder (15 g) was mixed with a homomixer at 2000 rpm for 30 minutes to prepare the main agent A.
<Mixing of main agent A and curing agent B>
The curing agent B was calcium hydroxide, and the amount added was 2 parts by mass with respect to 100 parts by mass of the main agent A. To mix the main agent A and the curing agent B, the main agent A and the curing agent B were placed on a pallet as shown in FIG. 4, and the main agent A and the curing agent B were added and mixed for 1 minute using a painting knife C as shown in FIG. After mixing, a cured product of Example 1 was obtained.

The curing agent B was calcium hydroxide, and the amount added was 10 parts by mass with respect to 100 parts by mass of the main agent A.

The curing agent B was alum, and the amount added was 10 parts by mass with respect to 100 parts by mass of the main agent A.

The curing agent B was baking soda (sodium hydrogen carbonate), and the amount added was 10 parts by mass with respect to 100 parts by mass of the main agent A.

The curing agent B was calcium hydroxide, and the amount added was 20 parts by mass with respect to 100 parts by mass of the main agent A.

The curing agent B was calcium hydroxide, and the amount added was 28 parts by mass with respect to 100 parts by mass of the main agent A.

The curing agent B was calcium hydroxide, and the amount added was 30 parts by mass with respect to 100 parts by mass of the main agent A.

The curing agent B was calcium hydroxide, and the amount added was 35 parts by mass with respect to 100 parts by mass of the main agent A.

(Comparative Example 1)
The composition of the main agent A was the same as that of Example 1, the curing agent B was calcium hydroxide, and the amount added was 0.5 parts by mass with respect to 100 parts by mass of the main agent A.

(Comparative Example 2)
The composition of the main agent A was the same as that of Example 1, the curing agent B was calcium hydroxide, and the amount added was 50 parts by mass with respect to 100 parts by mass of the main agent A. Since it is difficult to mix the main agent A and calcium hydroxide in this formulation, a mixture of 50 parts by mass of calcium hydroxide and 5 parts by mass of distilled water was used.

(Test Example 1) Measurement of hardness of each test sample (1) Adjustment method of test sample for hardness measurement The test sample for measurement is a 5 mm thick styrofoam plate with a 100 mm square hole, and paper is laid on the bottom surface. A mixture of the main agent A and the curing agent B was poured into the convex portion and hardened.

(2) Changes in hardness over time and measurement The hardness of the test sample for measurement was measured with DuroMeter (ASKER "Model CL-150"). This measuring device is a C type, and is used when the value measured by the A type (JIS K 6253-3 compliant) is 20 or less. The higher the value, the higher the hardness and the lower the flexibility.
The measurement was performed every 3 hours, 6 hours, 12 hours, 24 hours, 48 hours, and 96 hours after the test sample was prepared. Ten determined points were measured, and the average value was used as the measured value. The measurement environment was an indoor temperature of 23 ° C. and a humidity of 50%. The results are shown in FIG.

(Test Example 2) Measurement of water content of each test sample (1) Changes in water content over time The water content of each test sample is 12 hours, 24 hours, 36 hours, 2 days, 3 days after the test sample is prepared. It was measured by measuring the weight change every 4th, 6th, 11th, and 16th. For the amount of change in the amount of water, the rate of decrease in the amount of water contained in the main agent A (total amount of water: 18% by mass) was calculated. The results are shown in FIG.

Table 1 shows the formulations of each Example and Comparative Example, and the results of Test Example 1 and Test Example 2.

When the electrolyte of the curing agent B is calcium hydroxide, the cured product after 48 hours when the addition amount is 2 to 30 parts by mass exhibits elasticity and plasticity that can be freely deformed. There is. At this time, the hardness value of the durometer [C type] was 15.5 to 52.5. At this time, the surface condition was not cracked or wrinkled, but when the amount of calcium hydroxide added was 30 parts by mass, fine wrinkles were observed.
On the other hand, when the amount of calcium hydroxide added was 0.5 parts by mass, the adhesiveness still remained on the surface, and measurement with a durometer [C type] could not be performed. Further, when the amount of calcium hydroxide added was 50 parts by mass [a small amount of water was added], there was no elasticity and cracks were generated on the surface.

FIG. 1 shows the change in the hardness [durometer (C type)] of the main agent A with respect to the elapsed time after the addition of the curing agent B [calcium hydroxide] to the main agent A. The hardness value of each addition amount increases with the elapsed time, but the hardness value becomes saturated in about 48 hours. Further, it is shown that as the amount of the curing agent B added increases, the curing speed increases and the hardness value increases.

FIG. 2 shows the change in the amount of water evaporated in the main agent A with respect to the elapsed time after the addition of the curing agent B [calcium hydroxide] to the main agent A. In each addition amount, the amount of water evaporation increases with the elapsed time, and as the amount of the curing agent B added increases, the amount of water evaporation tends to decrease slightly. When the amount of the curing agent added is 50 parts by mass, the amount of water evaporation is larger than 30 parts by mass, because cracks occur from the initial stage of curing and the surface area of the main agent A increases. It is estimated to be.

FIG. 3 shows the relationship between the amount of water evaporation in the main agent A and the main agent A. The hardness of the main agent A increases as the amount of evaporation of water in the main agent A increases corresponding to the amount of each addition of the curing agent B.
However, it can be seen that the amount of water evaporated in the main agent A and the hardness of the main agent A are not directly related, but the amount of the curing agent B added determines the hardness of the main agent A.

From the results in Table 1, it was confirmed that the same effect as when the curing agent B was calcium hydroxide was confirmed when the curing agent B was alum or baking soda. In addition, although not shown in Table 1, magnesium chloride was confirmed to have the same effect.

(Test Example 3) Condition confirmation by bending of each test sample (1) Adjustment method of test sample for condition confirmation by bending For the test sample for condition confirmation by bending, a hole of 220 mm × 90 mm is made in a 10 mm thick styrofoam plate. A styrofoam plate is also laid on the bottom surface, and a mixture of main agent A and curing agent B is kneaded into the convex part to harden it, and the one 5 days after curing is cut to a width of 15 mm parallel to the long side with a cutter knife. Then, the long side was further divided into two equal parts and used as a test piece. The thickness dimension was 10 mm at the beginning of kneading, but decreased with the elapsed time after curing due to water evaporation, and the average value was 8.3 mm.
(2) Changes in the cured product by checking the state by bending 10 pieces of each of the test pieces (width 15 mm, thickness 8.3 mm (average value), length 110 mm) of the cured product of the present invention are round gauges (at an angle of 90 °). It was bent along the line provided with R), and it was visually observed whether cracks or breaks occurred on the outer periphery of the rounded portion. The results are shown in Table 2.

From the results of surface condition confirmation by bending in Table 2, when the curing agent B is 2 to 20 parts by mass with respect to 100 parts by mass of the main agent A, the surface condition is not wrinkled, the outer peripheral portion is not cracked, and there is no breakage. There wasn't. This result was the same for 2R and 5R gauges.
When the curing agent B was 28 parts by mass, it had sufficient bending characteristics, but some cracks were generated in the outer peripheral portion. In addition, all the 2R and 5R gauges were confirmed to be broken. When the amount of the curing agent B was 35 parts by mass, it was confirmed that the test sample was broken. In addition, all breaks were confirmed in 2R and 5R. Although not shown in Table 2, when the curing agent B was 1 part by mass with respect to 100 parts by mass of the main agent A, it did not solidify to a state where the test was possible in a time of 2 to 20 parts by mass.

(Test Example 4) Tensile test of each test sample (1) Preparation method of test sample for tensile test The test sample is a styrofoam plate with a thickness of 10 mm, a square hole of 220 mm × 90 mm is made, and a styrofoam plate is laid on the bottom surface. A mixture of the main agent A and the curing agent B is kneaded into the convex portion and hardened, and after 7 days of curing, the product is cut into a width of 15 mm parallel to the long side with a cutter knife, and the long side is further divided into two equal parts. Was used as a test piece. The test piece had a width of 15 mm, a thickness of 10 mm, and a length of 110 mm, and the length of the clamp portion was set to 30 mm each at the top and bottom, and was used for measuring the tensile strength of the cured product in the 55 mm length portion.
The thickness dimension was 10 mm at the beginning of kneading, but decreased with the elapsed time after curing due to water evaporation, and the average value was 8.3 mm.
Further, reinforcing plates were provided at the portions corresponding to the tensile test clamps at both ends of the test sample. The dimensions were a stainless steel plate having a length of 30 mm × 20 mm × a thickness of 0.8 mm, and the sample was bonded with the same agent with 30 mm in the length direction sandwiched from both sides of the sample.
(2) Measurement of Tensile Strength The tensile strength of the test piece was measured with a tensile tester (manufactured by A & D Co., Ltd., model number: RTF-1250). As a result of the tensile test, the maximum point load [N] and the maximum point elongation [% GL] are shown in Table 2. The test standard corresponds to JIS L 1096.
The maximum point load represents the maximum stress on the test piece. Further, as the maximum point elongation, the tensile elongation when the tensile strength showed the largest value when the tensile strength was measured was obtained as a percentage of the initial test length, and was used as the maximum point elongation. The maximum point elongation indicates that the larger the value, the better the elongation characteristics.
(Measurement conditions) Grip interval: 55 mm, humidity 65% RH, temperature 20 ° C, operation mode; single operation, operation direction: Up, movement speed: 100 mm / min, initial load removal operation: none, target load: 5N, Creep speed 10 mm / min, holding time: 3 seconds

From the results of the tensile test in Table 2, when the maximum point elongation (% GL) is 30% to 100%, very good elongation characteristics are shown, and the curing agent B is 2 with respect to 100 parts by mass of the main agent A. It was clarified that the content of about 20 parts by mass has excellent characteristics. It was shown that the hardness (hardness) at that time was 20 to 50, and the maximum point load (N) was 55N to 100N.

(Test Example 5) Measurement of hardness of each test sample (another method)
(1) Preparation method of test sample for hardness measurement For the test sample, a square hole of 220 mm × 90 mm is made in a 10 mm thick styrofoam plate, a styrofoam plate is laid on the bottom surface, and the main agent A and the curing agent B are formed on the convex portions. The mixture was kneaded and hardened, and after 7 days of curing, it was cut into a width of 15 mm parallel to the long side with a cutter knife, and the long side was further divided into two equal parts and used as a test piece.

(2) Changes in hardness over time and measurement The hardness of the test sample was measured by DuroMeter (ASKER "Model CL-150"). The measurement position was the central portion at a position 10 mm from the end of each sample. The results are shown in Table 2.

From the results in Table 2, it is shown that when the hardness of the durometer [C type] is 20 to 50, the cured product of the present invention is good, and more preferably 22 to 46.

(Test results)
(1) From the results in Table 1, when the amount of the curing agent B added to the main agent A is 2 to 20 parts by mass with respect to 100 parts by mass of the main agent A, the surface condition of the cured product of the present invention is good and the cured product can be cured. It became clear.
(2) From the results in Table 2, assuming that the amount of the curing agent B added to the main agent A is 2 to 20 parts by mass with respect to 100 parts by mass of the main agent A, the three-dimensional molded product of the present invention is suitable for "bending". It was revealed that it has the above-mentioned characteristics.
As described above, from the results of each test, the three-dimensional molded product of the present invention can be adjusted not only in hardness but also in maximum point elongation and maximum point weighting, and can be freely bent without surface cracking even when bent or pulled. It has been shown that it is a cured product having excellent flexibility and properties. In addition, it became clear that it is useful as in the usage state described later by utilizing the characteristics.

Immediately after mixing the main agent A and the curing agent B according to the present invention (this state is referred to as the "coating agent" of the present invention), the hardness is a slurry or soft clay, which is kneaded into a certain mold. Or, by overcoating itself, a cured product of the present invention having a desired thickness can be obtained, and a modeled product can be appropriately molded. In addition, paper, cloth, non-woven fabric, and aluminum are used for rough three-dimensional objects made of relatively strong materials such as metal / non-ferrous metal, wire rods such as plastics, strips, bamboo, and wood. It is also possible to cover the surface with a face material such as foil, apply the coating agent according to the present invention to a certain thickness on the surface material, and cure the coating material to create an appearance shape of a three-dimensional model.

Although it is not possible to deform a modeled product by a conventional modeling method, the present invention is characterized in that it can be freely deformed and modeled after being cured once by using the cured product or the modeling method of the present invention. Based on these characteristics, when metal or non-ferrous metal is used as an aggregate, it is desirable to take advantage of its plastic deformation and rub the surface of the cured product with a spatula with a curved surface (deform by applying pressure). It is possible to form irregularities in the shape.

(Usage example 1 of the embodiment)
As the main agent A, styrene-butadiene polymer emulsion (95 g), methylmethacryllate-butadiene polymer emulsion (95 g), polyethylene glycol (5 g), calcium carbonate-treated powder (275 g), zinc oxide-treated powder (zinc oxide-treated powder) 15 g) and titanium oxide-treated powder (15 g) were mixed in a homomixer at 2000 rpm for 30 minutes. The main agent A was made into a mass part 100, calcium hydroxide mass part 10 was added to the curing agent B, and the mixture was kneaded with a painting knife C for about 1 minute as shown in FIG.
A mixture (coating agent) of the main agent A and the curing agent B was applied to a model 6 (FIG. 6) previously formed using a steel wire having a diameter of 0.8 mm with a painting knife C as shown in FIG. .. FIG. 7 shows how the coating agent was cured after about 12 hours. The cured product could be shaped by hand as shown in FIG. In the state of FIG. 8, the adhesiveness of the surface of the main agent A was already lost at that time, and it could be freely bent together with the steel wire as an aggregate without adhering to the hand.

(Usage example 2 of the embodiment)
As the main agent A and the curing agent B, the same materials as in the above (Example 1 of use of the embodiment) were used. For the aggregate, make 20 hexagonal rings in advance using a steel wire with a diameter of 0.5 mm, and then assemble them in a spherical shape with an adhesive to complete an icosahedron, and a painting knife as in the case of 1 above. FIG. 9 shows a model that was smeared with D and made into a model. FIG. 10 shows a state in which the modeled object was left to stand for about 12 hours and then extremely distorted by hand. As described above, the mixture (coating agent) of the main agent A and the curing agent B followed the bending of the aggregate under any repeated bending, and cracking or peeling did not occur.

(Usage example 3 of the embodiment)
Among the decorations and tools used in temporary installations such as shows, events, and theater sets, for example, the conventional method for producing three-dimensional objects such as large rocks is to frame the frame with boards or cardboard. It was made by arranging it and pasting paper on it. However, with that method, it is quite difficult to create a skeleton for three-dimensionalization and a surface on it, and a lot of time and labor costs have been spent.
In addition, the conventional modeling method is to apply synthetic resin to glass fiber called FRP to make a tough model, but to change or modify the shape after molding, part of it is scraped or destroyed and re-formed. It will be modeled, but it cannot be easily modified because the material is hard.
Therefore, an example of producing a rock having a diameter of about 2 m using the present invention is shown in FIG.
Normally, a wire mesh that is rolled into a roll and is commercially available (a steel wire with a thickness of 0.8 mm and woven into a hexagon with a diagonal of about 2 cm) is made into an appropriate size (about 60 cm x 90 cm). Cut it and put some of it on top of each other to form a dome. In the case of wire mesh, since the thin wire is loosened at the end, it can be easily bonded to the overlapping part. In the case of wire mesh, by overlapping the surfaces of the wire mesh, a shell-shaped dome-shaped model that can withstand a considerable amount of external pressure was completed, and the surface was covered with cotton gauze to cover the entire surface.
Next, 100 parts by mass of the agent A and 20 parts by mass of the agent B of the present invention were well kneaded and applied to the surface of the dome with a trowel or the like to a thickness of 2 mm to 5 mm.
Since the cured product of the present invention can be freely deformed after curing, finely on the surface of the dome two days after application, using a spatula with a curved surface such as a finger or a spoon, utilizing the plastic deformation of the wire mesh. It was possible to create unevenness in the texture and add a rugged texture peculiar to rocks as shown in FIG.

FIG. 13 shows an example of manufacturing a pipe having a diameter of 150 mm and a thickness of about 5 mm using the present invention.
Conventionally, for example, in the case of manufacturing synthetic resin pipes, an extruder, peripheral equipment, and a die (die) are used, so that a considerable amount of production (minimum several hundred meters) is required for one production. This is because a considerable amount of production is required to be profitable in terms of dice production costs, equipment usage fees, labor costs for operation, and the like.
By using the method of the present invention, a pipe having a desired diameter can be manufactured in a desired amount in a single time. As an example of manufacturing, an example in which an aluminum alloy wire having a thickness of 2.6 mm is used for the core material forming the outer shape of the pipe is shown. When this wire is wound multiple times to a certain diameter (diameter about 150 mm) and stretched in the axial direction of a circle, the outer shape of the winding becomes a spiral, and a cloth (or a non-woven fabric made of synthetic resin) is wrapped around the spiral. Further, by applying the molding agent of the present invention on the pipe, the pipe can be easily shaped.
This pipe is expected to be used in various ways. For example, in stage decoration, it is used as a tree trunk, as a decoration that bends like a corner or a snake, as a work of art with the side surface of a pipe deformed, and as a functional member as a water pipe or a ventilation duct. be able to.

Further, the present invention can be applied to various things listed below. For example, for waterproof items, there are waterproof gloves / boots, aquariums, etc., and for items that require flexibility, apply it to a thin plate of wood, bamboo (1 mm to 0.1 mm), one side of paper, or between both. Extremely flexible surfaces can be manufactured.

FIG. 14 is an example of a painting. As the main agent A and the curing agent B, the same materials as those used in Example 1 of the above embodiment were used. In the wave part and the rock part, the mixing ratios of the main agent A and the curing agent B are different due to the ease of modeling. In the expression of waves, the softness of the mixture is required to express the shape of the swell. Since the mixture is required to have hardness in order to express it, the amount of the curing agent B is 30 parts by mass with respect to 100 parts by mass of the main agent A. Using a painting knife for both the wave part and the rock part, I was able to create a model that expresses the characteristics of the shape as shown in FIG. About 2 hours after the start of mixing the main agent A and the curing agent B, it is still at the start of curing, and it can be freely deleted and deformed. I was able to express myself freely. Six hours after the start of mixing the main agent A and the curing agent B, the adhesiveness of the surface is lost, and the storage state which is the same as that of the conventional oil painting is maintained.

Further, in the above-mentioned use example, after mixing the main agent A and the curing agent B in a predetermined ratio, the mixture is mixed with a commercially available acrylic paint [“Acrylic Paint Golden Aclicks” manufactured by Turner Color Co., Ltd.] to obtain a desired color. It can be colored uniformly. This is because the acrylic paint is made by kneading an acrylic resin (acrylic emulsion) and a pigment into a binder, and therefore has a high affinity with a mixture of the main agent A and the curing agent B in a predetermined ratio. Is.

<Potential for industrial use>
The three-dimensional molded product of the present invention can adjust not only hardness but also maximum point elongation and maximum point weight as appropriate, and has flexibility that allows free bending without surface cracking even when bent or pulled. It is useful because it can be molded as an excellent three-dimensional model.
In addition, paper, cloth, non-woven fabric, and aluminum foil are used for rough three-dimensional objects made of relatively strong materials such as metal / non-ferrous metals, wire rods such as plastics, strips, bamboo, and wood. It is also useful to cover the surface with a face material such as the above, apply the coating agent according to the present invention to a certain thickness, and cure the coating material to create an appearance shape as a three-dimensional model.

Although it is not possible to deform the modeled product by the conventional modeling method, it is possible to freely deform and model the product after it is cured by using the cured product or the production method of the present invention. For example, when metal or non-ferrous metal is used as an aggregate, the surface of the cured product is rubbed (deformed by applying pressure) on the surface of the cured product by taking advantage of its plastic deformation to form irregularities in a desired shape. Among the decorations and tools that can be used in temporary installations such as shows, events, and theater sets, for example, when making a three-dimensional object such as a large rock, the framework for making it three-dimensional and above it. It is also possible to create a surface on the surface, which is useful.

Further, by using the cured product of the present invention, for example, in the case of a synthetic resin pipe, a steel wire or a metal / non-woven metal wire such as aluminum / copper is wound multiple times to a certain diameter and wound in the axial direction of the circle. When stretched to, the outer shape of the winding becomes spiral, and a cloth (or a non-woven fabric made of synthetic resin) is wrapped around the spiral, and the curing agent of the present invention is used on the cloth to easily form a pipe. be able to.
The core material that forms the outer shape of this pipe is a linear or ribbon-shaped material (thin strip with a constant width) made of glass, carbon, synthetic resin, bamboo, wood, paper, cloth, etc., regardless of whether it is metal or non-ferrous metal. Alternatively, if it is a net or a planar material, it can be used as a core material. Further, the shape of the pipe can also be formed into a cone, a spindle, or an elliptical or polygonal cross section.
This pipe is expected to be used in various ways. For example, in stage decoration, it can be used as a tree trunk, as a decoration bent like a corner or a snake, as a work of art with the side surface of a pipe deformed, and as a functional member as a water pipe or a ventilation duct. It is useful.

Further, the cured product of the present invention includes, for example, waterproof gloves / boots, a water tank, etc. for waterproof materials, and is applied to one side of wood, bamboo thin plate or paper, or between both of them for those requiring flexibility. This is useful because it can be applied to the production of extremely flexible surfaces.

Since the main agent A imparts strong adhesiveness to itself, it has good adhesion to the coated surface, and the material cured by adding the curing agent B to the main agent A has elasticity similar to that of rubber. Because it does not crack or peel off and can withstand bending, it is possible to form a shaped object that follows the structure when it is applied to the structure, and the coating agent is cured. Before, it has strong adhesiveness and adhesive strength to objects that come into contact with it, but it has the property that the surface after curing is completely non-adhesive, and it has excellent waterproofness after curing. It is useful.

Furthermore, in paintings, in the case of expressing the shape of wave swell or sharp unevenness by using a coating agent with a different mixing ratio of the main agent A and the curing agent B in the three-dimensional wave part or rock part. By properly expressing the shape of a rock with a certain shape, it is possible to create a shape that expresses the characteristics of the desired shape with a painting knife for both the wave part and the rock part. About 2 hours after the start of mixing B, it is still at the start of curing, and it can be freely deleted and deformed. 6 hours after the start of mixing the main agent A and the curing agent B, the adhesiveness of the surface is lost, and it is possible to maintain the same storage state as the conventional oil painting, which is useful.

Further, since the main agent A is water-based, it is possible to mix commercially available acrylic paints and water-based paints, so that it is possible to freely create a color tone suitable for the purpose of expression, and it is cured according to the amount of the curing agent B added. Since materials having different speeds and elasticity can be freely obtained, relief-like paintings and three-dimensional modeling can be formed, so that it is possible to provide a cured product with rich expression, which is useful.

1 Main agent A
2 Hardener B
3 Pallet 4 Mixture 5 Painting knife C
6 Aggregate of shaped object using steel wire 7 Painting knife D
8 Shaped object smeared on aggregate 9 Modeled object with mixture applied to aggregate 10 Shaped object 11 Shaped object 11 Shaped object with mixture applied to regular icosahedron aggregate using steel wire 12 Deformed 11 sculptures 13 rock sculptures 14 rock surface irregularities 15 wire mesh 16 cloth (gauze)
17 Coating agent (mixture of main agent A and curing agent B)
18 Core material (aluminum alloy wire)
19 Cloth (nonwoven fabric)
20 Coating agent (mixture of main agent A and curing agent B)
21 Wave representation 22 Rock representation

Claims (7)

It is a three-dimensional molded product obtained by mixing and solidifying the main agent A and the curing agent B.
The main agent A contains an aqueous resin emulsion, an extender pigment, and a dispersant.
The resin of the aqueous resin emulsion is at least one selected from the group consisting of acrylic resin, acrylic acid ester copolymer, vinyl acetate resin, alkyd resin, phthalic acid resin, and urethane resin.
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogencarbonate, myoban, and magnesium chloride, and the amount of the curing agent B added is 100 parts by mass of the main agent A. A three-dimensional molded product, characterized in that the agent B is 2 to 20 parts by mass. The extender pigment is at least one selected from the group consisting of aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, alumina silicate, titanium oxide, and zinc oxide, and the amount of the extender pigment added is the main agent. The cured product according to claim 1, wherein the amount is 30 to 70% by mass based on the total amount of A. Either claim 1 or 2, wherein the dispersant is a polyacrylic acid-based dispersant, and the amount of the dispersant added is 1 to 10% by mass with respect to the entire main agent A. The cured product according to item 1. The cured product according to any one of claims 1 to 3, wherein the maximum point elongation (% GL) in the tensile test of the cured product is 30% to 100%. The cured product according to any one of claims 1 to 4, wherein the hardness of the cured product is 20 to 50 in a durometer hardness test (type C). The main agent A contains an aqueous resin emulsion, an extender pigment, and a dispersant.
The resin of the aqueous resin emulsion is at least one selected from the group consisting of acrylic resin, acrylic acid ester copolymer, vinyl acetate resin, alkyd resin, phthalic acid resin, and urethane resin.
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogen carbonate, alum, and magnesium chloride.
A coating agent in which 2 to 20 parts by mass of the curing agent B is mixed with 100 parts by mass of the main agent A is used.
(I) Metal / non-ferrous metal / plastic wire rod, metal / non-ferrous metal / plastic mesh material, or a three-dimensional member selected from bamboo or wood strip, or the surface of the member such as paper, cloth, non-woven fabric, aluminum foil, etc. A member whose surface is covered with a material; or (ii)
Metal / non-ferrous metal, glass, carbon, synthetic resin, bamboo, wood, paper, cloth, etc., linear or ribbon-shaped (thin strip with a certain width), net, surface-shaped core material, steel wire or A metal or non-ferrous metal wire such as aluminum or copper is wound multiple times to a certain diameter, stretched in the axial direction of the circle, the outer shape of the winding becomes spiral, and a non-woven cloth or synthetic resin is wrapped around the spiral. Attached pipe members; or (iii) thin plates of wood or bamboo, one side of paper, or both members;
A method for producing a three-dimensional model, which is characterized in that it is applied to the surface or between the surfaces of the surface and cured to form a cured product that can be deformed. The main agent A contains an aqueous resin emulsion, an extender pigment, and a dispersant.
The resin of the aqueous resin emulsion is at least one selected from the group consisting of acrylic resin, acrylic acid ester copolymer, vinyl acetate resin, alkyd resin, phthalic acid resin, and urethane resin.
The curing agent B contains at least one selected from the group consisting of calcium hydroxide, sodium hydrogen carbonate, alum, and magnesium chloride.
A coating agent in which 2 to 20 parts by mass of the curing agent B is mixed with 100 parts by mass of the main agent A is applied to the canvas, and can be freely deleted or deformed, or can be reapplied to create a painting or relief. A method of producing a painting, which is characterized by forming.

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